Activated carbon for hypersorber applications



2,829,115 I CARBON FOR HYPERSORBE APPLICATIONS Raymond M. Bushong and Harold .R. Cole, Fostoria,

Ohio, assignors to Union Carbide Corporation, a corporation of New York Application September 13, 1954 Serial No. 455,786

3 Claims. 01. 252-421 ACTIVATED No Drawing.

htates Patent gas streams by means of activated carbon. In processes of this type, the activated carbon is constantly in motion, and is elevated to the top of the hypersorber apparatus by means of a gas lift from which it is circulated downward through the hypersorber by gravity. Because of this moving bed motion, the activated particles undergo constant reduction in size, making it necessary that the activated carbon be hard, highly resistant to attrition, and highly adsorptive. Since carbon must be added continuously to compensate for physical and attrition losses, it is also necessary that a low cost carbon be employed.

Certain further limitations exist by reason of. the cost and availability of the raw materials from which activated carbon is made. Among these is the comparatively low density of some forms of activated carbon, which results in reduced adsorptive capacity; which factor is particularly disadvantageous when the carbon particles are of appreciable size. Another limitation resides in the fact that one of the forms of activated carbon is produced from coconut charcoal, which is costly, non-uniform in quality, and, at times, of low attrition resistance. For the reasons hereinabove mentioned, the ideal product for hypersorber applications is a relatively inexpensive activated carbon of high density, high adsorptive capacity, high attrition resistance, which is uniform in quality and can be prepared from readily available materials. I

. v '2 It is the object of this inventionfto provide suchan, activated carbon.

In accordance with the invention, this. object is attained by bonding and pelleting the blend of milled petroleum acid sludge coke flour and sulphur with a high-melting point pitch, preferably heating in dry steam, optionaly adding lubricating oil while maintaining an atmosphere of dry steam, pelleting, crushing and activat ing by any suitablemethod.

An important step in the process herein disclosed is that of mixing, and three embodiments thereof based on thermal conditions are possible. In so called hot mixing the binder is softened to a low viscosity to coat and bond the carbon particles. In cold or warm blending the pitch or binder is simply blended with the powder and sulphur to get a homogenous mixture with melting of pitch occurring with friction during the pelleting operation. Blending maybe performed in either a warm or cold mixer, preferably at 120 C. to 130? C. If the mix is cold, it must be passed .through the pellet mill two or three times to create suflicient heat to melt the pitch and bond the mix into well formed pellets. By heating the mix in a mixer during blending to a temperature just under the softening point of the pitch, less demand is made on the pellet mill to supply heat to the, mix, with the result that a single pass through the mill is sufficient. In warm mixing it is important to maintain the mixer temperature slightly below the softening point of the pitch used. If this temperature is exceeded, the pitch will soften and difiiculty will be caused by the mix building up on the mixer blades.

Cold or warm mixing is made possible'by using 7 to 18 parts of sulphur per parts of fixed carbon in the sludge coke flour. Sulphur acts as a lubricant, eliminating the necessity for oil or other type of lubricant. At temperatures of 130 C. or less, steam protection against oxidation in the mixer also can be eliminated. Binder concentrations can be reduced from 33 to 35 pounds of 175 C. melting point pitch to less than 30' pounds per 100 pounds of fixed carbon in the flour. For cold or warm mixing it is essential that-the pitch be milled to a flour; preferably about 60%fthrough 200 mesh with all through 35 mesh. The range of mixing and pelleting conditions for each of the three embodiments follows:

TABLE I Parts by Weight Mix'lypm'. Cold Warm Hot rom- To- From- To FrOm- To- Flnal Mix Temperature, 0 Room Temp. l60 Sludge Coke Flour, Parts Fixed Oarl bon 100 100 no Binder- O. M. P., C. 'I. Pitch, Parts/100 Parts Fixed Carbon in Flour 28 32 28 32 30 35 Sulphnr-Partsll00 Parts Fixed Oarbell in Flour 7 18 7 l8 7 I 18 Oil Lubricant- Parts/100 Parts Fixed Carbon in Flour 0 5 0 5 3 5 Number oi Passes Through Pellet A M 2 3 1 2 1 2 Patented Apr. 1, 1958 Because of the variation in fixed carbon in sludge coke, all weights in the above table are shown on the basis of fixed carbon in the sludge coke flour.

In the practice of the invention, the raw petroleum acid sludge coke is dried at a suitable temperature and milled to a hour. Elemental sulphur is added to the dried coke flour, a proportion which may range from about 7 parts to 18 parts by weight being added to about 100 parts of fixed carbon in the coke flour. This mixture is charged into a hot mixer and blended in an atmosphere of dry steam, which atmosphere is maintained throughout the mixing operation. High melting point pitch, which may be from either coal or wood distillation is added to the mixture in an amount which may range'from 30 parts to 35 .parts by weight to about 100 parts of fixed carbon in the coke flour, the mixing being continued until substantial blending is effected. Where necessary, lubricating oil is then added to the mixture in an amount which may range from about 3 parts to parts by weight to about 100 parts of fixed carbon in the coke flour, the

mixing being continued until substantial homogeneity of the mixture is assured. The ,final mix temperature may range from 160 C. to 170 C. The hot mixture is pelleted, crushed and the particles activated by any suitable method. The actual activation process may be CO gas, steam and/or flue gas, etc.

Illustrative of the invention, the following is a description of a successful production of activated carbons.

Raw petroleum acid sludge coke was dried at approximately 200 C. and milled to a fineness of about 60% through 200 mesh. To about 100 pounds, on a fixed carbon basis of the dry sludge coke flour was added about 8.8 pounds of sulphur, the mixture being charged into a hot mixer, and blended for about minutes. An atmosphere of dry steam was maintained in the mixer throughout the entire mixing operation. To the mixture was added about 35 pounds of 175 C. melting point pitch and the mixing continued until the mix temperature reached about 150 C. At this point about 5.1 pounds of lubricating oil was added and the mixing continued until-the mix temperature reached about 165 C. The mix was discharged while still hot and passed twice through a roll type pellet mill. After cooling, the pellets were sized such that after activation the product contained a maximum of 5% on 12 mesh and a maximum of 5% through 28 mesh using Tyler Standard Screen Scale sieves. The sized particles were then activated with CO in the conventional manner by heating for about 100 hours at about 1000 C.

Several tests, descriptions of which follow, were utilized to ascertain and demonstrate the superiority of the activated carbon of the invention, produced from sludge coke, with commercially available carbon made from coconut charcoal. l

The activity test to .which reference is made in the tables below determines the total amount of carbon tetrachloride which a given sample of carbon will pick up, and is expressed as the percentage of the weight of carbon sample tested. Dry air saturated with carbon tetrachloride at 0 C. is passed through a 10 centimeter bed of carbon in a tube until the carbon sample ceases to adsorb more carbon tetrachloride. The tube containing the carbon sample is immersed in a constant temperature water bath heldat C. When the carbon is completely saturated, it is removed from the machine and weighed. The weight in grams of carbon tetrachloride picked up, divided by the carbon weight in grams, multiplied by 100 is the percent activity.

The apparent density (vibrated) is a measure obtained by dividing the weight of carbon in grams by the volume of the same carbon in cubic centimeters when vibrated to refusal. In this test carbon is placed in a graduate and vibrated on an electric vibrator at a rate such as to give maximum settling, until the minimum volume is obtained.

A Apparent density (loose pack or bulk) .--This measure represents the weight of carbon in grams divided by its 1 weight in cubic centimeters as determined from a graduate without any tamping or vibration to refusal.

Butane and ethylene activity.--These tests establish the optimum carbon flow rate through, for example, a hypersorber, and require test apparatus of special design.

In running this test, approximately 1000 cc. of carbon are placed in a steam jacketed cylinder and dried by heating the carbon with preferably p. s. i. g. steam on the jacket while passing nitrogen "through the carbon charge. The drying period is complete when a cool mirror placed in the nitrogen exhaust stream shows only a trace of cloudiness. After dryingthe carbon is removed and the bulk density determined. The empty cylinder is then purged of nitrogen by passing butane through it. The dried carbon is then replaced in the cylinder and butane passed through the carbon charge at a rate of 0.1100. cubic feet per minute until 0.8 of a cubic foot of gas 13 discharged from the cylinder. The volume of gas adsorbed is determined by two wet test meters, one located ahead of the carbon and the other in the discharge line from the carbon. The volume of gas passed into the carbon minus the gas discharged from the carbon is the volume of gas adsorbed. To obtain the actual amount of gas adsorbed, corrections for gas and carbon temperature and gas pressure, and a factor for the particular gas used must be applied in the calculation.

The butane or ethylene activity is expressed in cc. of liquid butane or ethylene/cc. of activated carbon. It is also sometimes expressed as cc. of butane or ethylene/gm. of carbon as determined from the carbon bulk density.

Attrition l0ss.-The percentage loss in weight of carbon after completing 2000 cycles gives a numerical indication of the attrition or abrasion resistance of the carbon on test.

In running the tests, approximately 2000 cc. of dried and weighed carbon are placed in the attrition testing apparatus. The carbon is circulated through the system for 2000 cycles. The air for lifting the carbon from the bottom to the top of the unit is set at a flow rate of 17.5 cfm. After 2000 cycles through the system the carbon is removed and again dried. Dust and fine particles resulting from attrition are collected and screened over a 35 mesh Tyler standard sieve. The-ch35 mesh is added to the above carbon removed from the system. After drying, the carbon is weighed again and the loss in percent calculated. This is the attrition loss figure.

It will be seen from the foregoing data that the activated carbon of the invention is superior in density for a given activity and shows greater resistance to attrition than activated carbon made from coconut charcoal.

Another example of the invention demonstrating increased carbon activity is as follows; in this example the treatment was the same as previously set forth, but with the components varied as shown:

140 lbs. sludge coke flour 140 lbs. coconut charcoal flour. 39 lbs. C. M. P. coal tar pitch 34 lbs. 30 medium coal tar pitch. 9.7 lbs. sulphur 0 lb. sulphur.

Percent activity-87 percent--- 59 percent.

It will be seen from the above data that the use of sulphur in accordance with the invention increases the activity.

In another series of tests demonstrating the success 6 What is claimed is: v

1. The method of producing activated carbon of high density, large particle size, and high adsorptive capacity, which method comprises mixing in a vessel having heatof the invention, three different mixes were made. Mix 5 ing means, petroleum acid sludge coke flour and sul- A contained 400 pounds of sludge coke flour and 17S phur in a proportion by weight on a fixed carbon basis, pounds of 175 C. melting point coal tar pitch in flake from about 100 to 110 parts of said sludge colre to about form; mix B contained 400 pounds of sludge coke flour 9 parts of sulphur; heating said mixture to not more than and 154 pounds of 135 C. melting point hard wood 130 C., adding thereto from about 33 to 36 parts by pitch in lump form; mix C contained 120 pounds of weight of a binder selected from the group consisting of sludge coke flour and 34 pounds of 175 C. melting point coal tar pitch and wood tar pitch; heating said mixture coal tar pitch in milled form (100% through 35 mesh). to not more than 170 C.; pelleting and crushing said The amount of sulphur was varied in each of the mixes. mixture prior to activating the resulting particles. After activation, each product was tested for activity, 2. The method of producing activated carbon of high retentivity, apparent density and attrition loss. Test rey, g adsorptive p y and high attrition sults are reported in Table III below. sistance, which method comprises mixing petroleum acid TABLE III Mix A B C Sludge Coke Flour, Lbs 400 400 120 Sludge Coke Flour-Fixed Carbon, Lbs. 347 347 96 Binder, Type Binder, Lhs 170 154 34 Binder, Lbs./100 Fixed Carbon in Flour 49. 0 44.4 35.1

Sulphur, Lbs 3.5 18.7 35.7 9.2 18.5 35.4 8.5 16.9 25.4 Sulphur, LbsJlllO Lbs. Fixed CarboninFlour- 2.5 5.4 10.3 2.7 5.3 10.2 8.8 17.6 25.3 Activated Carbon Properties:

Vib..A.D .381 .395 .380 .412 .407 .411 .552 .510 .487

Attrition Loss 17.1 15.5 11.7 16.9 15.2 11.7 5.5 8.0 7.7

1 175 0. M. P., coal tar pitch.

a 135 C. M. P., hardwood pitch.

Mixes A and B show 'low retentivities and densities sludge coke flour and sulphur in a proportion by weight, as well as high attrition losses because of poor mixing on a fixed carbon basis, from about 100 to 110 parts of conditions. These two mixes were mixed to a final temsaid sludge coke to between 7 and 18 parts of said sulperature of 160 C. to 170 C. with no steam protecphur, heating said mixture to not more than 130 0., tion in the mixer. Because of the flake and lump pitch, adding to said mixture from about 33 to 36 parts by poor distribution of the mix components was achieved, weight of a binder selected from the group consisting and oxidation of the mix resulted. of coal tar pitch and wood tar pitch, heating said mix- Mix C was made by the cold blend process in which ture to not more than 170 C.; pelleting and crushing no heat was applied to the mix. The coke flour milled said mixture prior to activating the resulting particles. pitch and sulphur was simply blended in a cold bread- 3. The method of producing activated carbon, which type mixer for 20 minutes, after which 3.45 pounds of method comprises mixing in an atmosphere of substanoil lubricant were added. The mix was blended an adtially dry steam about parts by weight on a fixed ditiona'l ten minutes after adding the oil, and then carbon basis of petroleum acid sludge coke flour with passed through the pellet mill three times. The addition about 8 parts sulphur, heating said mixture not less than of oil lubricant, while not essential to the process, is 10 minutes at a temperature not above C.; adding helpful. to said mixture about 33 parts of a binder selected from It will be seen from Table III that increased amounts 50 the group consisting of a high melting point coal tar of sulphur increase the activity and reduce the attrition Pitch and a high melting 110mt Wood tar P 60min loss level for any given activity. The greatest increase uing said mixing and said heating to a temperature of in activity is obtained with a sulphur content of 18 to 20 not m a 0-; adding to s mi ture a out 4 pounds per 100 pounds of fixed carbon in the sludge parts lubricating oil and continuing said mixing and coke flour present in the mix. It will also be noted that 55 said heating to a temperature of not more than C.; approximately 9 pounds of sulphur per 100 pounds of maintaining said atmosphere of substantially dry steam fixed carbon in the flour produces maximum reduction in throughout said mixing and said heating; pelleting and attrition loss. It is also apparent from the above table crushing said mixture and activating said particles. that coal tar pitch having a melting point of C. produces a slightly lower attrition loss carbon than does 60 Refel'elmes Cited in the file of this Paltem the 135 C. melting point hard wood pitch.

While emphasis has been placed upon the use of the UNHED STATES PATENTS activated material subject of this invention in hyper- 177771.943 Thl'elfan 06L 7, sorber processes, other applications and uses thereof will 1,319,314 Zurchel' Aug. 18, 1931 be readily apparent to those skilled in the art, for ex- 1,925,438 Faben Sept. 5, 1933 ample, uses wherein a comparatively large particle size 34,769 McCulloch Mar. 11, 1941 activated carbon is desirable, since it is extremely dilfi- 1.362.463 Boehm et NOV. 1944 cult toactivate large carbonaceous particles without the 2,585,454 Gamson Feb. 12, 1952 sulphur treatment described above. 2,648,637 Rodman Aug. 11, 1953 

1. THE METHOD OF PRODUCING ACTIVATED CARBON OF HIGH DENSITY, LARGE PARTICLE SIZE, AND HIGH ADSORPTIVE CAPACITY, WHICH METHOD COMPRISES MIXING IN A VESSEL HAVING HEATING MEANS, PETROLEUM ACID SLUDGE COKE FLOUR AND SULPHUR IN A PROPORTION BY WEIGHT ON A FIXED CARBON BASIS, FROM ABOUT 100 TO 110 PARTS OF SAID SLUDGE COKE TO ABOUT 9 PARTS OF SULPHUR, HEATING SAID MIXTURE TO MORE THAN 130*C., ADDINT THERETO FROM ABOUT 33 TO 36 PARTS BY WEIGHT OF A BINDER SELECTED FROM THE GROUP CONSISTING OF COAL TAR PITCH AND WOOD TAR PITCH, HEATING SAID MIXTURE TO NOT MORE THAN 170*C., PELLETING AND CRUSHING SAID MIXTURE PRIOR TO ACTIVATING THE RESULTING PARTICLES. 